KR102375191B1 - Positive photosensitive siloxane resin composition and display device comprising the same - Google Patents

Abstract

The positive photosensitive siloxane resin composition according to an embodiment of the present invention comprises a) i) at least one reactive silane represented by the following Chemical Formula 1, and ii) at least one tetrafunctional reactive silane represented by the following Chemical Formula 2 under a catalyst. a siloxane-based copolymer having a polystyrene reduced weight average molecular weight (Mw) of 1,000 to 20,000 obtained by hydrolysis and condensation polymerization; b) 1,2-quinonediazide compounds; and c) a solvent.
(R ₁ )nSi(R ₂ ) _4-n [Formula 1]
Si(R ₃ ) ₄ [Formula 2]
Wherein R ₁ is each independently any one of an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, wherein R ₂ is an alkoxy group having 1 to 4 carbon atoms, phenoxy, or acetoxy, and R ₃ are each other It is independently any one of an alkoxy group having 1 to 4 carbon atoms, a phenoxy group, or an acetoxy group, and n is a natural number of 1 to 3.

Description

Positive photosensitive siloxane resin composition and display device including the same

The present invention relates to a positive photosensitive siloxane resin composition and a display device including the same.

In recent years, in liquid crystal display devices and organic light emitting diode displays, a photosensitive organic insulating film has been used to insulate between wirings disposed between layers and to improve an aperture ratio.

An acrylic insulating film is mainly used as an interlayer insulating film for a liquid crystal display, but there is a problem in outgassing due to a decrease in heat resistance. In addition, although a polyimide-based material is used as an interlayer insulating layer or a pixel defining layer for an organic light emitting diode display, there are problems in sensitivity, adhesion, transmittance, and heat discoloration resistance.

Accordingly, there is an increasing need for a material that suppresses gas emission and has a low moisture absorption rate in order to secure the reliability of the display device.

In order to solve these problems, the present invention provides a positive photosensitive siloxane resin composition having excellent performance such as sensitivity, resolution, adhesion, transmittance, and heat discoloration resistance, as well as suppressing gas release through excellent heat resistance and low moisture absorption. would like to provide

Another object of the present invention is to provide a display device having improved reliability by including an insulating film, a protective film, a planarization film, a barrier rib, a pixel defining film, and the like including the positive photosensitive siloxane resin composition.

A positive photosensitive siloxane resin composition according to an embodiment of the present invention for solving these problems includes a) i) at least one reactive silane represented by the following Chemical Formula 1, and ii) a tetrafunctional reactive silane represented by the following Chemical Formula 2 a siloxane-based copolymer having a polystyrene reduced weight average molecular weight (Mw) of 1,000 to 20,000 obtained by hydrolysis and condensation polymerization of at least one type under a catalyst; b) 1,2-quinonediazide compounds; and c) a solvent.

(R ₁ )nSi(R ₂ ) _4-n [Formula 1]

Si(R ₃ ) ₄ [Formula 2]

Wherein R ₁ is each independently any one of an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, wherein R ₂ is an alkoxy group having 1 to 4 carbon atoms, phenoxy, or acetoxy, and R ₃ are each other It is independently any one of an alkoxy group, phenoxy, or acetoxy group having 1 to 4 carbon atoms, and n is a natural number of 1 to 3.

In the siloxane-based copolymer, the content of the unreacted monomer may be 10% or less and the content of the catalyst may be 2000 ppm or less by removing the unreacted monomer and the catalyst.

The thermal decomposition temperature (Td) of the siloxane-based copolymer may be 450° C. or higher.

The siloxane-based copolymer may include a ladder structure, and the proportion of the siloxane-based copolymer having the ladder structure may be 30% or more of the total.

The siloxane-based copolymer may include 100 parts by weight, the 1,2-quinonediazide compound may include 5 to 50 parts by weight, and the solvent may have a solid content of 10 to 50% by weight.

The siloxane-based copolymer may be hydrolyzed and condensed by i) 20 to 80 parts by weight of the reactive silane represented by Formula 1, and ii) 20 to 80 parts by weight of the tetrafunctional reactive silane represented by Formula 2 above.

The siloxane-based copolymer may further include 5 to 50 parts by weight of a reactive silane represented by iii) the following formula (3).

(R ₄ ) _n Si(R ₅ ) _4-n [Formula 3]

wherein R ₄ is independently of each other vinyl, 3-acryloxyalkyl, 3-methacryloxyalkyl, 1-(p-hydroxyphenyl)alkyl, 2-(p-hydroxyphenyl)alkyl, 3-glycidoxyalkyl , 2-(3,4-epoxy cyclohexyl)alkyl, 3-isocyanatealkyl, oxetanealkyl, wherein R ₅ is an alkoxy group having 1 to 4 carbon atoms, phenoxy, or acetoxy, and n is 1 to 3 is a natural number.

The 1,2-quinonediazide compound is at least one of 1,2-quinonediazide 4-sulfonic acid ester, 1,2-quinonediazide 5-sulfonic acid ester, and 1,2-quinonediazide 6-sulfonic acid ester may include

The solvent is propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol methyl ether, Propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, dibutylene glycol dimethyl ether, and dibutylene glycol diethyl ether , Diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, diethylene glycol tertiary butyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol It may include at least one of ethylene glycol ethylhexyl ether, diethylene glycol methylhexyl ether, dipropylene glycol butyl methyl ether, dipropylene glycol ethylhexyl ether, and dipropylene glycol methylhexyl ether.

1 to 20 parts by weight of d) a silane coupling agent represented by the following Chemical Formula 4 may be further included.

(R ₆ ) _n Si(R ₇ ) _4-n [Formula 4]

wherein R ₆ are each independently 1-(p-hydroxyphenyl)alkyl, 2-(p-hydroxyphenyl)alkyl, 3-glycidoxyalkyl, 2-(3,4-epoxy cyclohexyl)alkyl, 3 -oxetane alkyl, 3-isocyanate alkyl, wherein R ₇ is an alkoxy group having 1 to 4 carbon atoms, phenoxy, or acetoxy, and n is a natural number of 1 to 3.

A method for preparing a positive photosensitive siloxane resin composition according to an embodiment of the present invention includes a) i) at least one reactive silane represented by the following formula (1), and ii) at least one tetrafunctional reactive silane represented by the following formula (2) is catalyzed Hydrolysis and condensation polymerization under the siloxane-based copolymer, b) a 1,2-quinonediazide compound; and c) forming a composition comprising a solvent, and filtering the siloxane-based copolymer to remove unreacted monomers and catalyst, wherein the siloxane-based copolymer has a polystyrene reduced weight average molecular weight (Mw) 1,000 to 20,000.

(R ₁ )nSi(R ₂ ) _4-n [Formula 1]

Si(R ₃ ) ₄ [Formula 2]

Wherein R ₁ is each independently any one of an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, wherein R ₂ is an alkoxy group having 1 to 4 carbon atoms, phenoxy, or acetoxy, and R ₃ are each other It is independently any one of an alkoxy group having 1 to 4 carbon atoms, a phenoxy group, or an acetoxy group, and n is a natural number of 1 to 3.

The filtering step may be repeated so that the content of the unreacted monomer is 10% or less and the content of the catalyst is 2000ppm or less.

An organic light emitting diode display according to an embodiment of the present invention includes an insulating substrate, a thin film transistor positioned on the insulating substrate, a first electrode connected to the thin film transistor, and a pixel positioned on the first electrode and partially exposing the first electrode a defining layer, an organic light emitting layer disposed on the pixel defining layer, and a second electrode disposed on the organic light emitting layer, wherein the pixel defining layer comprises a positive photosensitive siloxane resin composition, the positive photosensitive siloxane resin composition comprising: a) i) at least one reactive silane represented by the following formula (1), and ii) at least one tetrafunctional reactive silane represented by the following formula (2) in terms of polystyrene obtained by hydrolysis and condensation polymerization under a catalyst (Mw) These 1,000 to 20,000 siloxane-based copolymers; b) 1,2-quinonediazide compounds; and c) a solvent.

(R ₁ )nSi(R ₂ ) _4-n [Formula 1]

Si(R ₃ ) ₄ [Formula 2]

Wherein R ₁ is each independently any one of an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, wherein R ₂ is an alkoxy group having 1 to 4 carbon atoms, phenoxy, or acetoxy, and R ₃ are each other It is independently any one of an alkoxy group, phenoxy, or acetoxy group having 1 to 4 carbon atoms, and n is a natural number of 1 to 3.

The positive photosensitive siloxane resin composition as described above has excellent physical properties such as sensitivity, resolution, adhesion, transmittance and heat discoloration resistance, and can suppress gas release through excellent heat resistance and have low moisture absorption. In addition, a display device including the positive photosensitive siloxane resin composition may have improved reliability.

1 is a layout view of signal lines of a display unit of an organic light emitting diode display according to an exemplary embodiment.
2 is an equivalent circuit diagram of one pixel of a display unit according to an embodiment of the present invention.
3 is a cross-sectional view of one pixel of the organic light emitting diode display of FIG. 2 .

With reference to the accompanying drawings, the embodiments of the present invention will be described in detail so that those of ordinary skill in the art to which the present invention pertains can easily implement them. However, the present invention may be embodied in several different forms and is not limited to the embodiments described herein.

In order to clearly express various layers and regions in the drawings, the thicknesses are enlarged. Throughout the specification, like reference numerals are assigned to similar parts. When a part, such as a layer, film, region, plate, etc., is “on” another part, it includes not only cases where it is “directly on” another part, but also cases where there is another part in between. Conversely, when we say that a part is "just above" another part, we mean that there is no other part in the middle.

First, a positive photosensitive siloxane resin composition according to an embodiment of the present invention will be described below.

The positive photosensitive siloxane resin composition according to an embodiment of the present invention comprises a) i) at least one reactive silane represented by the following Chemical Formula 1, and ii) at least one tetrafunctional reactive silane represented by the following Chemical Formula 2 under a catalyst. A siloxane-based copolymer having a polystyrene reduced weight average molecular weight (Mw) of 1,000 to 20,000 obtained by removing unreacted monomers and catalysts after hydrolysis and condensation polymerization, b) a 1,2-quinonediazide compound, and c) a solvent can do.

(R ₁ )nSi(R ₂ ) _4-n [Formula 1]

Si(R ₃ ) ₄ [Formula 2]

Wherein R ₁ is each independently any one of an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, and R ₂ is independently of each other an alkoxy group having 1 to 4 carbon atoms, phenoxy, or acetoxy, and the R ₃ is each independently any one of an alkoxy group having 1 to 4 carbon atoms, phenoxy, or an acetoxy group, and n is a natural number of 1 to 3.

The positive photosensitive siloxane resin composition may include a) 100 parts by weight of the siloxane-based copolymer, b) 5 to 50 parts by weight of the 1,2-quinonediazide compound, and c) 10 to 50% by weight of the solid content of the solvent. can

The siloxane-based copolymer of a) used in the present invention not only has excellent performance such as sensitivity, resolution, adhesion, transmittance, and heat discoloration resistance, but also suppresses gas release with improved heat resistance and lowers moisture absorption. The reliability of the device can be improved.

A) i) the reactive silane represented by Formula 1 according to an embodiment of the present invention is phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane, phenylmethyldimethoxysilane, phenyltriacetoxy Silane, phenyltriphenoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiphenoxysilane, triphenylmethoxysilane, triphenylethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane , butyltrimethoxysilane, hexyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, and may be used alone or in a mixture of two or more.

A) i) The reactive silane represented by Formula 1 may be included in an amount of 20 to 80 parts by weight based on the total total monomers. If the content is less than 20 parts by weight, cracks may occur, and if it exceeds 80 parts by weight, it may be difficult to control the molecular weight due to poor reactivity during polymerization.

A) ii) the tetrafunctional reactive silane represented by Formula 2 used in the present invention may be tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetraacetoxysilane, and alone Or 2 or more types may be mixed and used.

A) ii) The tetrafunctional reactive silane represented by Chemical Formula 2 may be included in an amount of 20 to 80 parts by weight based on the total total monomers. When the content is less than 20 parts by weight, the solubility in aqueous alkali solution decreases when forming a pattern of the photosensitive siloxane resin composition, which may cause defects. This is because the siloxane oligomer may have excessive solubility in aqueous alkali solution.

In addition, the siloxane-based copolymer of a) according to an embodiment of the present invention iii) may further include a reactive silane represented by the following Chemical Formula 3, hydrolysis and condensation polymerization under a catalyst, and removing unreacted monomers and catalysts can be obtained

(R ₄ ) _n Si(R ₅ ) _4-n [Formula 3]

wherein R ₄ is independently of each other vinyl, 3-acryloxyalkyl, 3-methacryloxyalkyl, 1-(p-hydroxyphenyl)alkyl, 2-(p-hydroxyphenyl)alkyl, 3-glycidoxyalkyl , 2-(3,4-epoxy cyclohexyl)alkyl, 3-isocyanatealkyl, oxetanealkyl, wherein R ₅ is an alkoxy group having 1 to 4 carbon atoms, phenoxy, or an acetoxy group, and n is 1 to 3 is the natural number of

iii) The reactive silane represented by Formula 3 is, for example, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, 1-(p- Hydroxyphenyl)ethyltrimethoxysilane, 2-(p-hydroxyphenyl)ethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-gly Cydoxypropylmethyldimethoxysilane, 2-(3,4-epoxy cyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxy cyclohexyl)ethylmethyldimethoxysilane, 3-isocyanatepropyltriethoxysilane , 3-isocyanate propyltrimethoxysilane, may be oxetaneethyltrimethoxysilane, and may be used alone or in combination of two or more.

In the case of iii) the reactive silane represented by Chemical Formula 3 or a mixture thereof, the amount used may be 5 to 50 parts by weight of the total silane monomers. This is because, when the amount used is within the above range, adhesion and film curing degree are more excellent.

The oligomeric siloxane compound of a) used in the positive photosensitive siloxane resin composition of the present invention may be bulk polymerization or solution polymerization of reactive silane or the like with water and an acid or base catalyst under a catalyst, hydrolysis and condensation polymerization, It is obtained through the process of removing the reaction monomer and catalyst.

The acid catalyst that can be used for such polymerization may be hydrochloric acid, nitric acid, sulfuric acid, oxalic acid, formic acid, acetic acid, oxalic acid, propionic acid, butanoic acid, or pentanoic acid, and the base catalyst may be ammonia, organic amines and alkylammonium hydroxide salts. , can be used alone or in combination of two or more, simultaneously or in stages.

As a result of analyzing the finally obtained siloxane-based copolymer of a) using gel permeation chromatography (GPC), the polystyrene conversion weight average molecular weight (Mw) may be 1,000 to 20,000.

When the polystyrene reduced weight average molecular weight (Mw) is less than 1,000, in the evaluation of the positive photosensitive siloxane resin composition, the residual film ratio during the development process is lowered or the heat resistance is poor and the moisture absorption rate is weak. In addition, when the polystyrene conversion weight average molecular weight (Mw) exceeds 20,000, this is because the sensitivity of the positive photosensitive siloxane resin composition is lowered or the developability of the pattern is deteriorated.

In addition, the positive photosensitive siloxane resin insulating film composition of the present invention includes b) a 1,2-quinonediazide compound, and the 1,2-quinonediazide compound of b) according to an embodiment of the present invention is a photosensitive compound. can

The 1,2-quinonediazide compound may be, for example, 1,2-quinonediazide 4-sulfonic acid ester, 1,2-quinonediazide 5-sulfonic acid ester, or 1,2-quinonediazide 6-sulfonic acid ester. there is. As an example, b) the 1,2-quinonediazide compound may be a compound obtained by reacting a phenol compound with a naphthoquinonediazidesulfonic acid halogen compound. Specifically, the quinonediazide compound is a naphthoquinonediazidesulfonic acid halogenated compound. It may be a compound obtained by reacting the compound with a phenol compound represented by the following formula (5) under a weak base. In this case, the phenol compound may be used alone or in combination of two or more.

[Formula 5]

When synthesizing the quinonediazide compound with the phenolic compound and the naphthoquinonediazide sulfonic acid halogen compound as described above, the esterification degree may be about 50 to 85%. This is because, when the esterification degree is less than 50%, the residual film rate may deteriorate, and when it exceeds 85%, storage stability may be deteriorated.

The b) 1,2-quinonediazide compound may be included in an amount of 5 to 50 parts by weight based on 100 parts by weight of the siloxane-based copolymer of a). When the content is less than 5 parts by weight, the difference in solubility between the exposed part and the non-exposed part is small, making it difficult to form a pattern, and when it exceeds 50 parts by weight, a large amount of unreacted 1,2-quinonediazide compound is irradiated with light for a short time. This is because the remaining solubility in an aqueous alkali solution as a developer is too low, and development is difficult.

In addition, the positive photosensitive siloxane resin composition of the present invention includes c) a solvent, and the solvent of c) prevents flatness and coating stains of the positive photosensitive siloxane resin composition, thereby forming a uniform pattern profile. do.

The solvent of c) is, for example, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, Propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, dibutylene glycol dimethyl ether, and dibutyl Renglycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, diethylene glycol tertiary butyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol Diethyl ether, diethylene glycol ethyl hexyl ether, diethylene glycol methyl hexyl ether, dipropylene glycol butyl methyl ether, dipropylene glycol ethyl hexyl ether and dipropylene glycol methyl hexyl ether may be used alone or in combination of two or more can

The solvent of c) may be included so that the solid content of the positive photosensitive siloxane resin composition is 10 to 50 wt%. If the solid content is less than 10% by weight, the coating thickness becomes thin and the uniformity is lowered, and when it exceeds 50% by weight, the coating thickness becomes thick and it may put a strain on the coating equipment during coating. When the solid content of the total composition is 10 to 25 wt%, a slit coater is used, and when the solid content is 25 to 50 wt%, a spin coater or a slit coater and a spin coater (Slit and spin coater) Spin Coater) can be used.

The positive photosensitive siloxane resin composition of the present invention comprising the above components may further include d) a silane coupling agent represented by Chemical Formula 4 below.

(R ₆ ) _n Si(R ₇ ) _4-n [Formula 4]

R ₆ are each independently 1-(p-hydroxyphenyl)alkyl, 2-(p-hydroxyphenyl)alkyl, 3-glycidoxyalkyl, 2-(3,4-epoxy cyclohexyl)alkyl, ox cetane alkyl, 3-isocyanate alkyl, wherein R ₇ is an alkoxy group having 1 to 4 carbon atoms, phenoxy, or acetoxy, and n is a natural number of 1 to 3.

The positive photosensitive siloxane resin composition of the present invention as described above may be used after filtering with a 0.1 to 0.2 μm Millipore filter or the like with a solid concentration of 10 to 50 wt%.

The positive photosensitive siloxane resin composition described above has excellent physical properties such as sensitivity, resolution, adhesion, transmittance, and heat discoloration resistance.

Hereinafter, an organic light emitting display device including the above-described positive photosensitive siloxane resin composition will be described. 1 is a layout view of signal lines of a display unit of an organic light emitting diode display according to an exemplary embodiment, FIG. 2 is an equivalent circuit diagram of one pixel of the display unit according to an exemplary embodiment, and FIG. 3 is the organic light emitting diode display of FIG. It is a cross-sectional view of one pixel of a light emitting display device.

Referring to FIG. 1 , on the first display area LA of the substrate 100 , a first signal line 121 extending in one direction to transmit a scan signal, and a first signal line 121 crossing the first signal line 121 to transmit an image signal Two signal lines 171 are formed. The first signal line and the second signal line are connected to each pixel, and the pixel may be connected to various signal lines (not shown) to which other signals are applied in addition to the first and second signal lines.

On the substrate 100 , the driving unit 510 is positioned in the peripheral area PB outside the first display area LA and for controlling the thin film transistor of the pixel. The driver 510 may be mounted on the substrate 100 as an IC chip or may be integrated on the substrate together with the thin film transistor of the first display area LA.

Meanwhile, an organic light emitting diode display according to an exemplary embodiment includes a plurality of pixels each including an equivalent circuit as shown in FIG. 2 .

Referring to FIG. 2 , an organic light emitting diode display according to an exemplary embodiment includes a plurality of signal lines 121 and 171 and a plurality of pixels PX connected thereto and arranged in a substantially matrix form. include

The signal lines include a plurality of first signal lines 121 transmitting a gate signal (or a scan signal), a plurality of second signal lines 171 transmitting a data signal, and a plurality of third signal lines 172 transmitting a driving voltage Vdd. ) is included. The first signal line 121 extends approximately in the row direction and is substantially parallel to each other, and the second signal line 171 and the third signal line 172 intersect the first signal line 121 and extend in the column direction and are substantially parallel to each other. parallel

Each pixel PX includes a switching thin film transistor Q2, a driving thin film transistor Q1, a storage capacitor Cst, and an organic light emitting diode. , OLED) (70).

The switching thin film transistor Q2 has a control terminal, an input terminal, and an output terminal. The control terminal is connected to the first signal line 121 , the input terminal is connected to the second signal line 171 , and the output terminal is It is connected to the driving thin film transistor Q1. The switching thin film transistor Q2 transmits the data signal applied to the second signal line 171 to the driving thin film transistor Q1 in response to the scan signal applied to the first signal line 121 .

The driving thin film transistor Q1 also has a control terminal, an input terminal, and an output terminal, the control terminal is connected to the switching thin film transistor Q2, the input terminal is connected to the third signal line 172, the output terminal is It is connected to the organic light emitting device 70 . The driving thin film transistor Q1 flows an output current I _LD whose magnitude varies according to a voltage applied between the control terminal and the output terminal.

The capacitor Cst is connected between the control terminal and the input terminal of the driving thin film transistor Q1. The capacitor Cst charges the data signal applied to the control terminal of the driving thin film transistor Q1 and maintains it even after the switching thin film transistor Q2 is turned off.

The organic light emitting diode 70 has an anode connected to the output terminal of the driving thin film transistor Q1 and a cathode connected to a common voltage Vss. The organic light emitting diode 70 displays an image by emitting light with different intensity according to the output current I _LD of the driving thin film transistor Q1 .

3 is a cross-sectional view of one pixel of the organic light emitting diode display of FIG. 2 . In FIG. 3 , the stacking order will be described in detail with reference to the second thin film transistor Q2 and the organic light emitting diode 70 of FIG. 2 . Hereinafter, the second thin film transistor Q2 is referred to as a thin film transistor.

As shown in FIG. 3 , the organic light emitting diode display includes a substrate 100 , and a buffer layer 120 is positioned on the substrate 100 .

The buffer layer 120 may be formed as a single layer of silicon nitride (SiNx) or a double layer structure in which silicon nitride (SiNx) and silicon oxide (SiO ₂ ) are stacked. The buffer layer 120 serves to planarize the surface while preventing penetration of unnecessary components such as impurities or moisture.

A semiconductor 135 made of polysilicon is positioned on the buffer layer 120 .

The semiconductor 135 includes a channel region 1355 , a source region 1356 , and a drain region 1357 formed on both sides of the channel region 1355 , respectively. The channel region 1355 of the semiconductor is polycrystalline silicon undoped with impurities, that is, an intrinsic semiconductor. The source region 1356 and the drain region 1357 are polycrystalline silicon doped with conductive impurities, that is, an impurity semiconductor. The impurity doped into the source region 1356 and the drain region 1357 may be any one of a p-type impurity and an n-type impurity.

A gate insulating layer 140 is positioned on the semiconductor 135 . The gate insulating layer 140 may be a single layer or a plurality of layers including at least one of tetra ethyl ortho silicate (TEOS), silicon nitride, silicon oxide, and the above-described positive photosensitive siloxane resin composition.

A gate electrode 155 is positioned on the semiconductor 135 , and the gate electrode 155 overlaps the channel region 1355 .

The gate electrode 155 may be formed of a single layer or a plurality of layers of a low-resistance material or a material with strong corrosion, such as Al, Ti, Mo, Cu, Ni, or an alloy thereof.

A first interlayer insulating layer 160 is positioned on the gate electrode 155 . The material of the first interlayer insulating film 160, like the gate insulating film 140, may be tetra ethyl ortho silicate (TEOS), silicon nitride, silicon oxide, or the above-mentioned positive photosensitive siloxane resin composition, a single layer or It may be formed in multiple layers.

A source contact hole 66 and a drain contact hole 67 exposing the source region 1356 and the drain region 1357 respectively are formed in the first interlayer insulating layer 160 and the gate insulating layer 140 .

A source electrode 176 and a drain electrode 177 are positioned on the first interlayer insulating layer 160 . The source electrode 176 is connected to the source region 1356 through the contact hole 66 , and the drain electrode 177 is connected to the drain region 1357 through the contact hole 67 .

The source electrode 176 and the drain electrode 177 may be formed of a low-resistance material or a material with strong corrosion, such as Al, Ti, Mo, Cu, Ni, or an alloy thereof, as a single layer or a plurality of layers. For example, it may be a triple layer of Ti/Cu/Ti, Ti/Ag/Ti, and Mo/Al/Mo.

The gate electrode 155 , the source electrode 176 , and the drain electrode 177 are a control electrode, an input electrode, and an output electrode of FIG. 2 , respectively, and form a thin film transistor together with the semiconductor 135 . A channel of the thin film transistor is formed in the semiconductor 135 between the source electrode 176 and the drain electrode 177 .

A second interlayer insulating layer 180 is positioned on the source electrode 176 and the drain electrode 177 . The second interlayer insulating layer 180 includes a contact hole 82 exposing the drain electrode 177 .

The material of the second interlayer insulating film 180 may be tetra ethyl ortho silicate (TEOS), silicon nitride, silicon oxide, or the above-mentioned positive photosensitive siloxane resin composition, like the first interlayer insulating film, and may be a single layer or a plurality of layers. It can be formed in layers.

A first electrode 710 is positioned on the second interlayer insulating layer 180 . The first electrode 710 is electrically connected to the drain electrode 177 through the contact hole 82 , and the first electrode 710 may be an anode electrode of the organic light emitting diode of FIG. 2 .

In one embodiment of the present invention, an interlayer insulating film is formed between the first electrode 710 and the drain electrode 177 , but the first electrode 710 may be formed on the same layer as the drain electrode 177 , and the drain electrode It may be integral with (177).

A pixel defining layer 190 is positioned on the first electrode 710 . The pixel defining layer 190 has an opening 95 exposing the first electrode 710 . The pixel defining layer 190 may include polyacrylates, polyimides, or the above-described positive photosensitive siloxane resin composition and a silica-based inorganic material.

The organic emission layer 720 is positioned in the opening 95 of the pixel defining layer 190 .

The organic light emitting layer 720 includes a light emitting layer, a hole-injection layer (HIL), a hole-transporting layer (HTL), an electron-transporting layer (ETL), and an electron-injection layer (electron-injection layer, EIL) is formed in a plurality of layers including at least one.

When the organic emission layer 720 includes all of them, the hole injection layer is positioned on the first electrode 710 that is the anode electrode, and a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer may be sequentially stacked thereon.

In this case, the light emitting layer may be made of a low molecular weight organic material or a high molecular weight organic material such as PEDOT (Poly 3,4-ethylenedioxythiophene). The emission layer may include a red emission layer that emits red light, a green emission layer that emits green light, and a blue emission layer that emits blue light. image will be realized.

In addition, the light emitting layer may implement a color image by stacking a red light emitting layer, a green light emitting layer, and a blue light emitting layer together on a red pixel, a green pixel, and a blue pixel, and forming a red color filter, a green color filter, and a blue color filter for each pixel. . As another example, a color image may be implemented by forming a white light emitting layer emitting white light in all of the red pixel, the green pixel, and the blue pixel, and forming a red color filter, a green color filter, and a blue color filter for each pixel, respectively. When a color image is implemented using a white light emitting layer and a color filter, it is not necessary to use a deposition mask for depositing the red light emitting layer, the green light emitting layer, and the light emitting layer on each individual pixel, that is, a red pixel, a green pixel, and a blue pixel.

In addition, the white light emitting layer may be formed of a single light emitting layer emitting white light, and a plurality of light emitting layers emitting different colors may be stacked to emit white light. For example, a configuration enabling white light emission by combining at least one yellow light emitting layer and at least one blue light emitting layer, a configuration enabling white light emission by combining at least one cyan light emitting layer and at least one red light emitting layer, at least one magenta light emitting layer It may also include a configuration that enables white light emission by combining the light emitting layer and at least one green light emitting layer.

A second electrode 730 is positioned on the pixel defining layer 190 and the organic emission layer 720 .

The second electrode 730 becomes a cathode electrode of the organic light emitting diode. Accordingly, the first electrode 710 , the organic light-emitting layer 720 , and the second electrode 730 form the organic light-emitting device 70 .

Depending on the direction in which the organic light emitting diode 70 emits light, the organic light emitting diode display may have any one of a front display type, a rear display type, and a double-sided display type.

Next, the encapsulation member 260 is positioned on the second electrode 730 .

The encapsulation member 260 may be formed by alternately stacking one or more organic layers and one or more inorganic layers. Each of the inorganic layer or the organic layer may be plural.

The organic layer is formed of a polymer, and preferably a single film or a laminate film formed of any one of polyethylene terephthalate, polyimide, polycarbonate, epoxy, polyethylene, and polyacrylate. More preferably, the organic layer may be formed of polyacrylate, and specifically, a monomer composition including a diacrylate-based monomer and a triacrylate-based monomer is polymerized. The monomer composition may further include a monoacrylate-based monomer. In addition, a known photoinitiator such as TPO may be further included in the monomer composition, but is not limited thereto.

The inorganic layer may be a single layer or a stacked layer including a metal oxide or a metal nitride. Specifically, the inorganic layer may include any one of SiNx, Al ₂ O ₃ , SiO ₂ , and TiO ₂ .

The uppermost layer exposed to the outside among the encapsulation layers may be formed of an inorganic layer to prevent moisture permeation to the organic light emitting device.

As described above, the organic light emitting diode display according to an embodiment of the present invention may include an insulating layer, a protective layer, and a pixel defining layer including the positive photosensitive siloxane resin composition. In addition, although the present specification has described the positive photosensitive siloxane resin composition used in an organic light emitting display device, the present specification is not limited thereto and may be used in any display device.

Such a positive photosensitive siloxane resin composition may be formed as an insulating film having a pattern or the like through the following method.

First, the positive photosensitive siloxane resin composition according to an embodiment of the present invention is applied to a substrate by spin coating, slit and spin coating, slit coating, or roll coating method. After drying in vacuum, the solvent is removed through pre-baking to form a coating film. In this case, the pre-bake may be performed at a temperature of about 100 to 120° C. for 1 to 3 minutes.

Then, a predetermined pattern is formed by irradiating the coating film with visible light, ultraviolet light, far ultraviolet light, electron beam or X-ray according to a previously prepared pattern, and developing with a developer to remove unnecessary portions.

It is preferable to use an aqueous alkali solution as the developer, and for example, inorganic alkalis such as sodium hydroxide, potassium hydroxide, and sodium carbonate, primary amines such as ethylamine, n-propylamine, and secondary amines such as diethylamine and n-propylamine Tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine, and triethylamine Alcoholamines such as dimethylethanolamine, methyldiethanolamine and triethanolamine or tetramethylammonium hydroxide and tetraethylammonium hydroxide It may be an aqueous solution of a quaternary ammonium salt.

In this case, the developer is used by dissolving an alkaline compound at a concentration of about 0.1 to 5 parts by weight, and may further include a water-soluble organic solvent such as methanol or ethanol and a surfactant.

In addition, after developing with the developer, it is washed with ultrapure water for about 30 to 90 seconds to remove unnecessary parts and dried to form a pattern. After irradiating light such as ultraviolet rays to the formed pattern again, the final pattern can be obtained by heating the pattern at a temperature of about 150 to 400° C. for about 30 to 90 minutes using a heating device such as an oven.

Hereinafter, a positive photosensitive siloxane resin composition according to an embodiment of the present invention and a comparative example will be described. This specification only exemplifies preferred examples to help the understanding of the present invention, and the scope of the present invention is not limited to the following examples.

Synthesis example One ( siloxane Preparation of copolymer (A))

In a flask equipped with a cooling tube and a stirrer, 55 parts by weight of phenyltriethoxysilane, 20 parts by weight of tetraethoxysilane, and 25 parts by weight of methyltriethoxysilane, respectively, as reactive silanes, 100 parts by weight of methanol as a solvent, and nitrogen substitution After that, it was gently stirred.

50 parts by weight of ultrapure water and 4 parts by weight of oxalic acid as a catalyst were additionally added to the reaction solution, and then gently stirred again. After about 1 hour, the reaction solution was heated to 60° C., maintained at this temperature for 10 hours for polymerization, and then cooled to room temperature to complete the reaction.

Then, it was further quenched below 0 °C to remove the synergistic solution containing unreacted monomers and catalysts through precipitation of the reactants. Methanol was further added and the purification process was repeated until unreacted monomers and catalyst were completely removed.

After the purification process, the residual alcohol-based solvent and residual moisture generated during the reaction were removed through vacuum drying. Finally, a siloxane-based copolymer (A) having a polystyrene reduced weight average molecular weight (M _W ) of 3000 was prepared.

Synthesis example 2 ( siloxane Preparation of copolymer (B))

In a flask equipped with a cooling tube and a stirrer, as reactive silanes, 60 parts by weight of butyltrimethoxysilane and 40 parts by weight of tetramethoxysilane were added, and after nitrogen substitution, the mixture was gently stirred. 50 parts by weight of ultrapure water and 2 parts by weight of oxalic acid as a catalyst were added to the reaction solution, and then gently stirred again. After about 1 hour, the reaction solution was heated to 60° C. and maintained at this temperature for 10 hours. After bulk polymerization, the reaction was terminated by cooling to room temperature.

Further, by quenching below 0 °C, the synergistic solution containing unreacted monomers and catalysts was removed through precipitation of the reactants. Methanol was further added and the purification process was repeated until unreacted monomers and catalyst were completely removed.

After the purification process, the residual alcohol-based solvent and residual moisture generated during the reaction were removed through vacuum drying. Through this, a siloxane-based copolymer (B) having a polystyrene reduced weight average molecular weight (M _W ) of 7000 was prepared.

Synthesis example 3 ( siloxane Preparation of copolymer (C))

In Synthesis Example 1, 30 parts by weight of n-butyltriethoxysilane, 50 parts by weight of tetramethoxysilane, and 20 parts by weight of 3-glycidoxypropyltriethoxysilane as reactive silanes, respectively, in a flask equipped with a cooling tube and a stirrer in Synthesis Example 1 It was carried out in the same manner as in Synthesis Example 1, except that it was added. Through this, a siloxane-based copolymer (C) having a polystyrene reduced weight average molecular weight (M _W ) of 5000 was prepared.

Synthesis example 4 ( siloxane Preparation of copolymer (D))

In Synthesis Example 2, 50 parts by weight of benzyltrimethoxysilane, 40 parts by weight of tetraacetoxysilane, and 10 parts by weight of 1-(p-hydroxyphenyl)propyltrimethoxysilane as reactive silanes in a flask equipped with a cooling tube and a stirrer in Synthesis Example 2 It was carried out in the same manner as in Synthesis Example 2, except that parts by weight were added. Through this, a siloxane-based copolymer (D) having a polystyrene reduced weight average molecular weight (M _W ) of 10000 was prepared.

Synthesis example 5 ( siloxane Preparation of copolymer (E))

It was carried out in the same manner as in Synthesis Example 1, except that 50 parts by weight of tolyltriethoxysilane and 50 parts by weight of tetraethoxysilane were put in a flask equipped with a cooling tube and a stirrer as reactive silanes in Synthesis Example 1, respectively. Through this, a siloxane-based copolymer (E) having a polystyrene reduced weight average molecular weight (M _W ) of 6000 was prepared.

Synthesis example 6 ( siloxane Preparation of copolymer (F))

It was carried out in the same manner as in Synthesis Example 1, except that 50 parts by weight of silyltriethoxysilane and 50 parts by weight of tetramethoxysilane were put in a flask equipped with a cooling tube and a stirrer as reactive silanes in Synthesis Example 1, respectively. Through this, a siloxane-based copolymer (F) having a polystyrene reduced weight average molecular weight (M _W ) of 5500 was prepared.

Synthesis example 7 ( siloxane Preparation of copolymer (G))

In Synthesis Example 2, it was carried out in the same manner as in Synthesis Example 2, except that 20 parts by weight of n-hexyltriethoxysilane and 80 parts by weight of tetraethoxysilane were put into a flask equipped with a cooling tube and a stirrer as reactive silanes, respectively. did Through this, a siloxane-based copolymer (G) having a polystyrene conversion weight average molecular weight (M _W ) of 19000 was prepared.

Synthesis example 8 ( siloxane Preparation of copolymer (H))

It was carried out in the same manner as in Synthesis Example 1, except that 30 parts by weight of phenyltriethoxysilane and 70 parts by weight of tetraethoxysilane were put in a flask equipped with a cooling tube and a stirrer as reactive silanes in Synthesis Example 1, respectively. Through this, a siloxane-based copolymer (H) having a polystyrene reduced weight average molecular weight (M _W ) of 14000 was prepared.

Synthesis example 9 ( siloxane Preparation of copolymer (I))

In Synthesis Example 1, 70 parts by weight of diphenyldimethoxysilane, 20 parts by weight of tetraethoxysilane, and 10 parts by weight of 3-isocyanate propyltriethoxysilane were put in a flask equipped with a cooling tube and a stirrer as reactive silanes, respectively. was carried out in the same manner as in Synthesis Example 1. Through this, a siloxane-based copolymer (I) having a polystyrene reduced weight average molecular weight (M _W ) of 2500 was prepared.

Synthesis example 10 (1,2- quinonediazide Preparation of compound (A))

1 mol of the phenol compound represented by the following formula (6) and 2 mol of 1,2-naphthoquinonediazide-5-sulfonic acid [chloride] are subjected to a condensation reaction, 1,2-naphthoquinonediazide having an esterification degree of 67%- A 5-sulfonic acid ester compound was prepared.

[화학식 6]

[Formula 6]

Synthesis example 11 (1,2- quinonediazide Preparation of compound (B))

1 mol of the phenol compound represented by the following formula (7) and 2 mol of 1,2-naphthoquinonediazide-5-sulfonic acid [chloride] were subjected to a condensation reaction, and 1,2-naphthoquinonediazide-5- having an esterification degree of 80% A sulfonic acid ester compound was prepared.

[화학식 7]

[Formula 7]

Comparative Synthesis Example One ( siloxane Preparation of copolymer (J))

It was carried out in the same manner as in Synthesis Example 2, except that 10 parts by weight of silyltriethoxysilane and 90 parts by weight of tetraethoxysilane were added as reactive silanes to a flask equipped with a cooling tube and a stirrer in Synthesis Example 2, respectively. Through this, a siloxane-based copolymer (J) having a polystyrene reduced weight average molecular weight (M _W ) of 25000 was prepared.

Comparative Synthesis Example 2 ( siloxane Preparation of copolymer (K))

In the same manner as in Synthesis Example 1, except that in Synthesis Example 1, 70 parts by weight of phenyltriethoxysilane and 30 parts by weight of n-hexyltrimethoxysilane were put into a flask equipped with a cooling tube and a stirrer as reactive silanes, respectively. carried out. Through this, a siloxane-based copolymer (K) having a polystyrene reduced weight average molecular weight (M _W ) of 3000 was prepared.

Comparative Synthesis Example 3 ( siloxane Preparation of copolymer (L))

In Synthesis Example 2, it was carried out in the same manner as in Synthesis Example 2, except that 90 parts by weight of butyltriethoxysilane and 10 parts by weight of tetraethoxysilane were put into a flask equipped with a cooling tube and a stirrer as reactive silanes, respectively. Through this, a siloxane-based copolymer (L) having a polystyrene reduced weight average molecular weight (M _W ) of 1500 was prepared.

Comparative Synthesis Example 4 ( siloxane Preparation of copolymer (M))

In Synthesis Example 2, after the polymerization was completed, the same method as in Synthesis Example 2 was carried out, except that the synergistic solution containing unreacted monomers and catalyst was not removed. Through this, a siloxane-based copolymer (M) having a polystyrene reduced weight average molecular weight (M _W ) of 7000 was prepared.

Comparative Synthesis Example 5 (Preparation of acrylic copolymer (A))

A mixed solution of 400 parts by weight of tetrahydrofuran, 30 parts by weight of methacrylic acid and 30 parts by weight of styrene, and 40 parts by weight of glycidyl methacrylate was added to a flask equipped with a cooler and a stirrer. After the liquid composition was sufficiently mixed in a mixing vessel, 15 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) was further added.

The polymerization mixture solution was slowly raised to 55 °C, maintained at this temperature for 24 hours, cooled to room temperature, and 500 ppm of hydrobenzophenone was added as a polymerization inhibitor to obtain a polymer solution having a solid content of 30 wt%.

Then, 100 parts by weight of the polymer solution was precipitated using 1000 parts by weight of n-hexane to remove unreacted monomers in the polymer solution. After precipitation, the solution in which the unreacted material was dissolved was removed through a filtration process using a mesh. Thereafter, vacuum drying was performed at 30 degrees or less to remove solvents containing unreacted monomers remaining even after the filtration process. Through this, an acrylic copolymer (A) having a polystyrene conversion weight average molecular weight (MW) of 8000 was prepared.

Comparative Synthesis Example 6 ( imide Preparation of copolymer (A))

In a flask equipped with a cooler and a stirrer, 70 parts by weight of gamma-butyrolactone, 100 parts by weight of 4,4'-diamino-3,3'-dimethyl-diphenylmethane as diamine, 2,2-bis ( 100 parts by weight of 3,4-anhydrodicarboxyphenyl) hexafluoropropane was added to a reaction vessel, and the reaction was stirred at room temperature for 1 hour. To terminate the reaction at the end, 20 parts by weight of phthalic anhydride was additionally added, followed by further reaction at room temperature for 1 hour, and then the reaction was terminated. Through this, an imide-based copolymer (A) having a polystyrene conversion weight average molecular weight (MW) of 10000 was prepared.

Example 1 (Preparation of positive photosensitive siloxane resin composition )

Put 100 parts by weight of the siloxane-based copolymer (A) prepared in Synthesis Example 1 and 25 parts by weight of the 1,2-naphthoquinonediazide compound (A) prepared in Synthesis Example 10, so that the solid content is 25 parts by weight After mixing and dissolving with propylene glycol methyl ether acetate, it was filtered through a 0.1 μm Millipore filter to prepare a positive photosensitive siloxane resin composition.

Example 2 (Preparation of positive photosensitive siloxane resin composition )

It was prepared in the same manner as in Example 1, except that the siloxane-based copolymer (B) of Synthesis Example 2 was used instead of the siloxane-based copolymer (A) of Synthesis Example 1 in Example 1.

Example 3 (Preparation of positive photosensitive siloxane resin composition )

It was prepared in the same manner as in Example 1, except that the siloxane-based copolymer (C) of Synthesis Example 3 was used instead of the siloxane-based copolymer (A) of Synthesis Example 1 in Example 1.

Example 4 (Preparation of positive photosensitive siloxane resin composition )

It was prepared in the same manner as in Example 1, except that the siloxane-based copolymer (D) of Synthesis Example 4 was used instead of the siloxane-based copolymer (A) of Synthesis Example 1 in Example 1.

Example 5 (Preparation of positive photosensitive siloxane resin composition )

It was prepared in the same manner as in Example 1, except that the siloxane-based copolymer (E) of Synthesis Example 5 was used instead of the siloxane-based copolymer (A) of Synthesis Example 1 in Example 1.

Example 6 (Preparation of positive photosensitive siloxane resin composition )

It was prepared in the same manner as in Example 1, except that the siloxane-based copolymer (F) of Synthesis Example 6 was used instead of the siloxane-based copolymer (A) of Synthesis Example 1 in Example 1.

Example 7 (Preparation of positive photosensitive siloxane resin composition )

It was prepared in the same manner as in Example 1, except that the siloxane-based copolymer (G) of Synthesis Example 7 was used instead of the siloxane-based copolymer (A) of Synthesis Example 1 in Example 1.

Example 8 (Preparation of positive photosensitive siloxane resin composition )

It was prepared in the same manner as in Example 1, except that the siloxane-based copolymer (H) of Synthesis Example 8 was used instead of the siloxane-based copolymer (A) of Synthesis Example 1 in Example 1.

Example 9 (Preparation of positive photosensitive siloxane resin composition )

It was prepared in the same manner as in Example 1, except that the siloxane-based copolymer (I) of Synthesis Example 9 was used instead of the siloxane-based copolymer (A) of Synthesis Example 1 in Example 1.

Example 10 (Preparation of positive photosensitive siloxane resin composition )

In Example 1, in place of the 1,2-naphthoquinonediazide-5-sulfonic acid ester compound (A) of Synthesis Example 10, the 1,2-naphthoquinonediazide-5-sulfonic acid ester compound of Synthesis Example 11 ( It was prepared in the same manner as in Example 1, except that B) was used.

Example 11 (Preparation of positive photosensitive siloxane resin composition )

Example 1 was carried out in the same manner as in Example 1, except that 5 parts by weight of 2-(3,4-epoxy cyclohexyl)ethyltrimethoxysilane was additionally used as a silane coupling agent when preparing the photosensitive resin composition in Example 1. A photosensitive resin composition was prepared.

comparative example 1 (positive photosensitivity) siloxane resin composition preparation)

It was prepared in the same manner as in Example 1, except that the siloxane-based copolymer (J) of Comparative Synthesis Example 1 was used instead of the siloxane-based copolymer (A) of Synthesis Example 1 in Example 1.

comparative example 2 (positive photosensitivity) siloxane resin composition preparation)

It was prepared in the same manner as in Example 1, except that the siloxane-based copolymer (K) of Comparative Synthesis Example 2 was used instead of the siloxane-based copolymer (A) of Synthesis Example 1 in Example 1.

comparative example 3 (positive photosensitivity) siloxane resin composition preparation)

It was prepared in the same manner as in Example 1, except that the siloxane-based copolymer (L) of Comparative Synthesis Example 3 was used instead of the siloxane-based copolymer (A) of Synthesis Example 1 in Example 1.

comparative example 4 (positive photosensitivity) siloxane resin composition preparation)

It was prepared in the same manner as in Example 1, except that the siloxane-based copolymer (M) of Comparative Synthesis Example 4 was used instead of the siloxane-based copolymer (A) of Synthesis Example 1 in Example 1.

comparative example 5 (Preparation of positive photosensitive acrylic resin composition)

It was prepared in the same manner as in Example 1, except that the acrylic copolymer (A) of Comparative Synthesis Example 5 was used instead of the siloxane-based copolymer (A) of Synthesis Example 1 in Example 1.

comparative example 6 (Preparation of positive photosensitive polyimide resin composition)

It was prepared in the same manner as in Example 1, except that the imide-based copolymer (A) of Comparative Synthesis Example 6 was used instead of the siloxane-based copolymer (A) of Synthesis Example 1 in Example 1.

For Examples 1 to 11 and Comparative Examples 1 to 6 described above, physical properties such as sensitivity, resolution, adhesion, transmittance, heat discoloration resistance, moisture absorption and heat resistance were measured and shown in Table 1 below.

After applying the positive photosensitive siloxane resin composition and the positive photosensitive acrylic resin composition prepared in Examples 1 to 11 and Comparative Examples 1 to 5 on a glass substrate using a spin coater, vacuum drying Then, it was pre-baked on a hot plate at 100° C. for 2 minutes to form a film having a thickness of 4.0 μm.

A) Sensitivity: After irradiating an ultraviolet ray having an intensity of 20 mW/cm 2 to form a 5 μm contact hole using a predetermined pattern mask on the film formed as above, tetramethylammonium hydroxide 2.38 wt% was developed for 1 minute at 23 °C with an aqueous solution of , and washed with ultrapure water for 1 minute.

Then, the pattern developed above was irradiated with ultraviolet light having an intensity of 20 mW/cm2 and 500 mJ/cm2 was cured in an oven at 230° C. for 60 minutes to obtain a pattern film having a thickness of 3.5 μm and a contact hole size of 5 μm. .

At this time, the amount of irradiation for forming a 5 μm contact hole was measured.

B) Resolution: The minimum size of the contact hole formed during the sensitivity measurement in step A) was measured.

C) Adhesive strength: A pattern film was formed in the same manner as in the sensitivity measurement in A), but the adhesive strength according to the bake temperature was compared based on the case where the 10 μm line width and the slit width were 1:1. At this time, the case in which the adhesive force is secured at 90 ° C. to 100 ° C pre-baking is indicated by ○, the case where the adhesion force is ensured in the pre-bake 105 to 115 ° C. did

D) Transmittance: For the evaluation of transmittance, the transmittance of the pattern film formed during the measurement of sensitivity in A) was measured at 400 nm using a spectrophotometer. At this time, the case where the transmittance was 90% or more was denoted by ○, the case of 85 to 90% was denoted by △, and the case of less than 80% was denoted by ×.

E) Heat discoloration resistance: The heat discoloration resistance due to a change in transmittance of 400 nm before and after curing was evaluated by additionally curing the measuring substrate for transmittance evaluation in D) for 60 minutes in an oven at 300°C. At this time, a case where the change rate was less than 5% was denoted by ○, a case in which it was 5 to 10% was denoted by △, and a case in which it exceeded 10% was denoted by ×.

F) Moisture absorption: Measure the weight change before and after dipping the pattern film formed in the same way as in the sensitivity measurement of A) in a constant temperature water bath at 25 ° C for 24 hours, and moisture absorption through this rate was evaluated. At this time, a case where the change rate was less than 0.1% was denoted by ○, a case in which it was 0.1 to 0.5% was denoted by △, and a case in which it exceeded 0.5% was denoted by ×.

G) Heat resistance: Heat resistance was measured using TGA. After sampling the pattern film formed during the sensitivity measurement in A), the temperature was raised from room temperature to 900 °C at a rate of 10 °C per minute using TGA. The case where the thermal decomposition temperature (Td) is 450 °C or higher is indicated by ○, the case where the thermal decomposition temperature (Td) is 350 to 400 °C is indicated by △, and the case where the thermal decomposition temperature (Td) is less than 350 °C is indicated by ×.

division Sensitivity
(mJ/cm ² ) resolution
(um) adhesion permeability heat resistance
discoloration moisture
moisture absorption heat resistance Example 1 70 2 ○ ○ ○ ○ ○ Example 2 75 2 ○ ○ ○ ○ ○ Example 3 70 2 ○ ○ ○ ○ ○ Example 4 70 2 ○ ○ ○ ○ ○ Example 5 75 2 ○ ○ ○ ○ ○ Example 6 75 2 ○ ○ ○ ○ ○ Example 7 75 2 ○ ○ ○ ○ ○ Example 8 75 2 ○ ○ ○ ○ ○ Example 9 70 2 ○ ○ ○ ○ ○ Example 10 80 2 ○ ○ ○ ○ ○ Example 11 75 2 ○ ○ ○ ○ ○ Comparative Example 1 140 3 × ○ ○ × ○ Comparative Example 2 135 3 × ○ ○ × × Comparative Example 3 125 3 × ○ ○ × × Comparative Example 4 80 3 × ○ ○ × × Comparative Example 5 140 3 ○ ○ × × × Comparative Example 6 150 3 × × × △ △

Through Table 1, the positive photosensitive siloxane resin compositions prepared in Examples 1 to 11 according to the present invention were excellent in sensitivity compared to Comparative Examples 1 to 3 and Comparative Examples 5 to 6, and the resolution compared to Comparative Examples 1 to 6 Excellent. In addition, the adhesive strength was excellent compared to Comparative Examples 1 to 4 and Comparative Example 6, the transmittance compared to Comparative Example 6, and the heat discoloration resistance compared to Comparative Examples 5 to 6 was excellent. In particular, compared with Comparative Examples 1 to 6, improved reliability was secured by suppressing gas release due to excellent heat resistance and maintaining a low moisture absorption rate.

Through this evaluation, it was confirmed that only the positive photosensitive siloxane resin compositions prepared in Examples 1 to 11 were possible as materials satisfying all of the above seven physical properties.

Next, the amount of unreacted monomer and catalyst included in the positive photosensitive siloxane resin composition according to an embodiment of the present invention will be described. The amount of unreacted monomer is measured by gas chromatography (GC), and the amount of the residual catalyst is measured by ion chromatography (IC).

A) Sensitivity - A case where the amount of UV irradiation for forming a 5um-sized contact hole pattern was 80mJ or less, ○, 80 ~ 100mJ, △, and an X, exceeding 100mJ.

B) Resolution - The minimum size of the contact hole pattern (Pattern) formed when measuring the sensitivity of A) was measured. A case with a minimum size of 2 μm or less was denoted by ○, and a case with a minimum size of 3 μm or more was denoted by X.

C) Moisture Absorption - Moisture absorption was evaluated by measuring the change in weight before and after immersing the pattern in a constant temperature water bath at 25° C. for 24 hours. At this time, the case where the rate of change was less than 0.1% was denoted by ○, the case where the rate of change was 0.1 to 0.5% was denoted by △, and the case where it exceeded 0.5% was denoted by X.

unreacted monomer 8% 8% 7% 9% 5% 4% 7% 3% catalyst Hydrochloric acid 2000ppm 1450ppm nitric acid 1120ppm oxalic acid Acetic acid 1460ppm Hydrochloric acid 2200ppm Nitric acid 2360ppm 2740 ppm oxalic acid Acetic acid 2230ppm Sensitivity 80mJ 75mJ 73mJ 72mJ 105mJ 115mJ 105mJ 112mJ ○ ○ ○ ○ X X X X resolution 2μm 2μm 2μm 2μm 3μm 4μm 3μm 3μm ○ ○ ○ ○ X X X X moisture absorption 0.09% 0.08% 0.08% 0.06% 0.13% 0.27% 0.17% 0.23% ○ ○ ○ ○ △ △ △ △

unreacted monomer 10% 12% 15% 13% 15% 11% 13% 14% catalyst 1250ppm hydrochloric acid 950 ppm nitric acid 1340 ppm oxalic acid Acetic acid 1215ppm hydrochloric acid 3250ppm 950 ppm nitric acid 1340 ppm oxalic acid Acetic acid 1215ppm Sensitivity 78mJ 75mJ 77mJ 78mJ 76mJ 75mJ 78mJ 80mJ ○ ○ ○ ○ ○ ○ ○ ○ resolution 2μm 3μm 4μm 3μm 4μm 3μm 3μm 4μm ○ X X X X X X X moisture absorption 0.05% 0.06% 0.07% 0.06% 0.57% 0.16% 0.21% 0.24% ○ ○ ○ ○ X △ △ △

According to Tables 2 to 3, the examples in which hydrochloric acid is 2200 ppm, nitric acid is 2360 ppm, oxalic acid is 2740 ppm, and acetic acid is 2230 ppm, as catalysts, the physical properties for sensitivity and resolution were not appropriate, Moisture absorption was also poor.

In addition, it was confirmed that the examples in which the amount of unreacted monomer was 10% or more were also not suitable for resolution or moisture absorption.

That is, according to the above table, it was confirmed that the positive photosensitive siloxane resin composition having an unreacted monomer content of 10% or less and a catalyst content of 2000 ppm or less can provide appropriate sensitivity, resolution, and moisture absorption.

Although preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concept of the present invention as defined in the following claims are also provided. is within the scope of

100: flexible substrate 120: buffer layer
121: first signal line 135: semiconductor
1355: channel region 1356: drain region
140: gate insulating film 155: gate electrode
160: interlayer insulating film 171: second signal line
172: third signal line 176: source electrode
177: drain electrode 180: interlayer insulating film
200: first display unit 260: encapsulation member
510: driving unit 1000: display device

Claims (24)

a) i) at least one reactive silane represented by the following formula (1), and ii) at least one tetrafunctional reactive silane represented by the following formula (2) in terms of polystyrene obtained by hydrolysis and condensation polymerization under a catalyst (Mw) These 1,000 to 20,000 siloxane-based copolymers;
b) 1,2-quinonediazide compounds; and
c) a solvent;
including,
The siloxane-based copolymer,
A positive photosensitive siloxane resin composition having an unreacted monomer content of 10% or less and a catalyst content of 2000 ppm or less:
(R ₁ )nSi(R ₂ ) _4-n [Formula 1]
Si(R ₃ ) ₄ [Formula 2]
Wherein R ₁ is each independently any one of an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, wherein R ₂ is an alkoxy group having 1 to 4 carbon atoms, phenoxy, or acetoxy, and R ₃ are each other It is independently any one of an alkoxy group having 1 to 4 carbon atoms, a phenoxy group, or an acetoxy group, and n is a natural number of 1 to 3.
delete In claim 1,
A positive photosensitive siloxane resin composition wherein the thermal decomposition temperature (Td) of the siloxane-based copolymer is 450° C. or higher. In claim 1,
The siloxane-based copolymer includes a ladder structure,
A positive photosensitive siloxane resin composition in which the proportion of the siloxane-based copolymer having the ladder structure is 30% or more of the total. In claim 1,
The siloxane-based copolymer includes 100 parts by weight, the 1,2-quinonediazide compound includes 5 to 50 parts by weight, and the solvent has a solid content of 10 to 50% by weight of the positive photosensitive siloxane resin composition. In claim 1,
The siloxane-based copolymer,
A positive photosensitive siloxane resin composition obtained by hydrolysis and condensation polymerization of i) 20 to 80 parts by weight of the reactive silane represented by Formula 1, and ii) 20 to 80 parts by weight of the tetrafunctional reactive silane represented by Formula 2 above. In claim 1,
The siloxane-based copolymer is
iii) A positive photosensitive siloxane resin composition further comprising 5 to 50 parts by weight of a reactive silane represented by the following formula (3):
(R ₄ ) _n Si(R ₅ ) _4-n [Formula 3]
wherein R ₄ is independently of each other vinyl, 3-acryloxyalkyl, 3-methacryloxyalkyl, 1-(p-hydroxyphenyl)alkyl, 2-(p-hydroxyphenyl)alkyl, 3-glycidoxyalkyl , 2-(3,4-epoxy cyclohexyl)alkyl, 3-isocyanatealkyl, oxetanealkyl, wherein R ₅ is an alkoxy group having 1 to 4 carbon atoms, phenoxy, or acetoxy, and n is 1 to 3 is a natural number. In claim 1,
The 1,2-quinonediazide compound is at least one of 1,2-quinonediazide 4-sulfonic acid ester, 1,2-quinonediazide 5-sulfonic acid ester, and 1,2-quinonediazide 6-sulfonic acid ester A positive photosensitive siloxane resin composition comprising a. In claim 1,
The solvent is propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol methyl ether, Propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, dibutylene glycol dimethyl ether, and dibutylene glycol diethyl ether , Diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, diethylene glycol tertiary butyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol A positive photosensitive siloxane resin composition comprising at least one of ethylene glycol ethylhexyl ether, diethylene glycol methylhexyl ether, dipropylene glycol butyl methyl ether, dipropylene glycol ethylhexyl ether, and dipropylene glycol methylhexyl ether. In claim 1,
A positive photosensitive siloxane resin composition further comprising 1 to 20 parts by weight of d) a silane coupling agent represented by the following Chemical Formula 4:
(R ₆ ) _n Si(R ₇ ) _4-n [Formula 4]
wherein R ₆ are each independently 1-(p-hydroxyphenyl)alkyl, 2-(p-hydroxyphenyl)alkyl, 3-glycidoxyalkyl, 2-(3,4-epoxy cyclohexyl)alkyl, 3 -oxetane alkyl, 3-isocyanate alkyl, wherein R ₇ is an alkoxy group having 1 to 4 carbon atoms, phenoxy, or acetoxy, and n is a natural number of 1 to 3. a) i) at least one reactive silane represented by the following formula (1), and ii) at least one tetrafunctional reactive silane represented by the following formula (2) is hydrolyzed and condensation-polymerized under a catalyst to form a siloxane-based copolymer, b) 1, 2-quinonediazide compounds; and c) forming a composition comprising a solvent, and
A filtration step of removing unreacted monomers and catalysts with respect to the siloxane-based copolymer,
The filtration step is repeated so that the content of the unreacted monomer is 10% or less and the content of the catalyst is 2000ppm or less,
The method for preparing a positive photosensitive siloxane resin composition wherein the siloxane-based copolymer has a polystyrene reduced weight average molecular weight (Mw) of 1,000 to 20,000:
(R ₁ )nSi(R ₂ ) _4-n [Formula 1]
Si(R ₃ ) ₄ [Formula 2]
Wherein R ₁ is each independently any one of an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, wherein R ₂ is an alkoxy group having 1 to 4 carbon atoms, phenoxy, or acetoxy, and R ₃ are each other It is independently any one of an alkoxy group, phenoxy, or acetoxy group having 1 to 4 carbon atoms, and n is a natural number of 1 to 3.
delete In claim 11,
A method for producing a positive photosensitive siloxane resin composition wherein the thermal decomposition temperature (Td) of the siloxane-based copolymer is 450° C. or higher. In claim 11,
The siloxane-based copolymer includes a ladder structure,
The method for producing a positive photosensitive siloxane resin composition, wherein the ratio of the siloxane-based copolymer having the ladder structure is 30% or more of the total. In claim 11,
The siloxane-based copolymer includes 100 parts by weight, the 1,2-quinonediazide compound includes 5 to 50 parts by weight, and the solvent has a solid content of 10 to 50% by weight. Preparation of a positive photosensitive siloxane resin composition method. In claim 11,
The siloxane-based copolymer,
I) 20 to 80 parts by weight of the reactive silane represented by the formula (1), and ii) 20 to 80 parts by weight of the tetrafunctional reactive silane represented by the formula (2) hydrolysis and condensation polymerization of a positive photosensitive siloxane resin composition. In claim 11,
The siloxane-based copolymer is
iii) A method for preparing a positive photosensitive siloxane resin composition further comprising 5 to 50 parts by weight of a reactive silane represented by the following Chemical Formula 3:
(R ₄ ) _n Si(R ₅ ) _4-n [Formula 3]
wherein R ₄ is independently of each other vinyl, 3-acryloxyalkyl, 3-methacryloxyalkyl, 1-(p-hydroxyphenyl)alkyl, 2-(p-hydroxyphenyl)alkyl, 3-glycidoxyalkyl , 2-(3,4-epoxy cyclohexyl)alkyl, 3-isocyanatealkyl, oxetanealkyl, wherein R ₅ is an alkoxy group having 1 to 4 carbon atoms, phenoxy, or acetoxy, and n is 1 to 3 is a natural number. In claim 11,
d) A method for producing a positive photosensitive siloxane resin composition further comprising 1 to 20 parts by weight of a silane coupling agent represented by the following Chemical Formula 4:
(R ₆ ) _n Si(R ₇ ) _4-n [Formula 4]
wherein R ₆ are each independently 1-(p-hydroxyphenyl)alkyl, 2-(p-hydroxyphenyl)alkyl, 3-glycidoxyalkyl, 2-(3,4-epoxy cyclohexyl)alkyl, 3 -oxetane alkyl, 3-isocyanate alkyl, wherein R ₇ is an alkoxy group having 1 to 4 carbon atoms, phenoxy, or acetoxy, and n is a natural number of 1 to 3. insulated substrate,
a thin film transistor positioned on the insulating substrate;
a first electrode connected to the thin film transistor;
a pixel defining layer positioned on the first electrode and partially exposing the first electrode;
an organic light emitting layer positioned on the pixel defining layer, and
a second electrode positioned on the organic light emitting layer;
The pixel defining layer includes a positive photosensitive siloxane resin composition,
The positive photosensitive siloxane resin composition,
a) i) at least one reactive silane represented by the following formula (1), and ii) at least one tetrafunctional reactive silane represented by the following formula (2) in terms of polystyrene obtained by hydrolysis and condensation polymerization under a catalyst (Mw) These 1,000 to 20,000 siloxane-based copolymers;
b) 1,2-quinonediazide compounds; and
c) a solvent;
including,
The siloxane-based copolymer,
An organic light emitting diode display having an unreacted monomer content of 10% or less and a catalyst content of 2000 ppm or less:
(R ₁ )nSi(R ₂ ) _4-n [Formula 1]
Si(R ₃ ) ₄ [Formula 2]
Wherein R ₁ is each independently any one of an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, wherein R ₂ is an alkoxy group having 1 to 4 carbon atoms, phenoxy, or acetoxy, and R ₃ are each other It is independently any one of an alkoxy group, phenoxy, or acetoxy group having 1 to 4 carbon atoms, and n is a natural number of 1 to 3.
delete In paragraph 19,
The siloxane-based copolymer includes 100 parts by weight, the 1,2-quinonediazide compound includes 5 to 50 parts by weight, and the solvent has a solid content of 10 to 50% by weight. In paragraph 19,
The siloxane-based copolymer,
An organic light emitting display device obtained by hydrolysis and condensation polymerization of i) 20 to 80 parts by weight of the reactive silane represented by Formula 1, and ii) 20 to 80 parts by weight of the tetrafunctional reactive silane represented by Formula 2 above. In paragraph 19,
The siloxane-based copolymer is
iii) an organic light emitting display device further comprising 5 to 50 parts by weight of a reactive silane represented by the following Chemical Formula 3:
(R ₄ ) _n Si(R ₅ ) _4-n [Formula 3]
wherein R ₄ is independently of each other vinyl, 3-acryloxyalkyl, 3-methacryloxyalkyl, 1-(p-hydroxyphenyl)alkyl, 2-(p-hydroxyphenyl)alkyl, 3-glycidoxyalkyl , 2-(3,4-epoxy cyclohexyl)alkyl, 3-isocyanatealkyl, oxetanealkyl, wherein R ₅ is an alkoxy group having 1 to 4 carbon atoms, phenoxy, or acetoxy, and n is 1 to 3 is a natural number. In paragraph 19,
The positive photosensitive siloxane resin composition,
An organic light emitting display device further comprising 1 to 20 parts by weight of d) a silane coupling agent represented by the following Chemical Formula 4:
(R ₆ ) _n Si(R ₇ ) _4-n [Formula 4]
wherein R ₆ are each independently 1-(p-hydroxyphenyl)alkyl, 2-(p-hydroxyphenyl)alkyl, 3-glycidoxyalkyl, 2-(3,4-epoxy cyclohexyl)alkyl, 3 -oxetane alkyl, 3-isocyanate alkyl, R ₇ is an alkoxy group having 1 to 4 carbon atoms, phenoxy, or acetoxy, and n is a natural number of 1 to 3.

Images